Resonant ion-dip infrared spectroscopy has been used to record size-specific infrared spectra of C6H6-(H2O)(n) clusters with n = 1 through 7 in the O-H stretch region. The O-H stretch spectra show a dramatic dependence on cluster size. For the n = 3 to 5 clusters, the transitions can be divided into three types-attributable to free, pi hydrogen-bonded, and single donor water-water O-H stretches-consistent with a C6H6-(H2O)(n) structure in which benzene is on the surface of a cyclic (H2O)(n) cluster. In n = 6 and 7 clusters, the spectra show distinct new transitions in the 3500 to 3600 wave number region. After comparison of these results with the predictions of ab initio calculations on (H2O)(n) clusters, these new transitions have been assigned to double donor O-H stretches associated with the formation of a more compact, noncyclic structure beginning with (H2O)(6). This is the same size cluster for which ab initio calculations predict that a changeover to noncyclic (H2O)(n) structures will occur.